Hindered amine light stabilizer hydrazides

ABSTRACT

New and novel carboxylic acid hydrazides bearing a 2,2,6,6-tetra-alkyl-4-piperidine ring and new and novel polymeric compositions stabilized therewith are provided. The novel compounds which contain a light stabilizing group and a reactive hydrazide functionality in the same molecule are prepared by hydrazinolysis of the ester group of an intermediate carboxylic acid ester which contains the 2,2,6,6-tetralkylpiperidine moiety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to derivatives ofN-(2,2,6,6-tetraalkyl-4-piperidinyl)-containing carboxylic acidhydrazides. These compounds are very efficient in the stabilization ofpolymeric systems which are subject to degradation upon exposure to heatand/or light. These compounds contain both a hindered amine lightstabilizing group and an acid hydrazide or derivative thereof. The acidhydrazide derivative enhances the photooxidative stabilizing propertiesof the hindered amine groups and contributes thermooxidative stabilizingand metal complexing properties to the compounds.

2. Description of the Prior Art

Hindered amine light stabilizers bearing carboxylic acid hydrazidefunctionality (hereinafter HALS-hydrazides) and derivatives thereof areknown. There are five examples in the literature where the hinderedamine moiety and the hydrazide moiety (--C(═O)--NH--NH₂) are present inthe same molecule. ##STR1##

Derivatives of these HALS-hydrazides are disclosed in several patents.U.S. Pat. Nos. 4,145,512 and 4,178,279 teach the reaction ofHALS-hydrazide groups with isocyanate groups of polyisocyanates ofisocyanate prepolymers to obtain light stabilized polyurethanes. U.S.Pat. No. 4,336,183 discloses acyl derivatives of HALS-hydrazides. U.S.Pat. No. 4,824,884 discloses cyclic anhydride derivatives of the parentN-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acid hydrazides (of U.S. patentapplication Ser. No. 310,408). These derivatives are also efficient heatand light stabilizers for polymeric systems but do not fall under thescope of this invention.

U.S. Pat. No. 4,396,735 discloses mixtures of hindered amine lightstabilizers and heterocyclic acid hydrazides for stabilizing syntheticresin compositions. Such systems are described as synergistic, since thecombination is better than the hindered amine alone, and the hydrazidealone is not a light stabilizer.

In addition to activity as a stabilizer, commercially useful stabilizeradditives must have both excellent compatibility with and/or solubilityin the polymeric substrates to be stabilized along with superiorresistance to loss from the stabilized composition during processing andend-use application. Many stabilizer additives exhibit limitedcompatibility in certain substrates and excessive tendency to exude,sublime and/or volatilize during weathering or processing of thestabilized composition. A major problem often exists when use conditionsrequire prolonged exposure to elevated temperatures. Therefore, severalattempts have been made to increase the compatibility and reduce thevolatility of such stabilizer additives in various resin systems bymodifying their structures. While improvements have been noted over theyears, experience has shown that state-of-the-art stabilizers do notexhibit the desired combination of properties in all resins. Continuedevolution of new polymeric compositions guarantees the need foradditional structural modifications on any potential heat and/or lightstabilizer intended for use. The versatility of the HALS-hydrazidesdisclosed herein allows for adaptation of the stabilizer combination tosuit such new compositions.

The novel HALS-hydrazides of the instant invention are reactivehydrazides, capable of forming typical hydrazide derivatives. They canreact with a variety of functional groups to permit property adjustment(such as compatibility and volatility). By careful selection of theproper derivative, one can increase the compatibility of the novelcompounds with various host resins to be stabilized. The novelderivatives have low volatility and are not readily lost from polymericsystems via volatilization, migration or extraction. For example theyreact with cyclic anhydrides with formation of imides or amic acids;esters or acid halides with formation of acyl hydrazides; ketones andaldehydes with formation of hydrazones; chloroformates with formation ofsemicarbazates; and isocyanates with formation of semicarbazides. Thediacyl hydrazide function (formed by reaction of the hydrazide with ananhydride, ester or acid halide) is, known to be particularly resistantto thermal degradation and a particularly useful antioxidant function(U.S. Pat. No. 3,639,334).

Polymers such as polyolefins (e.g. polyethylene, polypropylene, etc.)styrenics (e.g. polystyrene, rubber modified polystyrene, ABS, MBSetc.), polyvinyl chloride, polycarbonates, polyesters, polyphenyleneethers and polyamides for example are subject to degradation anddiscoloration upon exposure to heat and/or light with consequentdeterioration of their mechanical properties. Various stabilizers havebeen proposed to inhibit such deterioration. Hindered piperidine lightstabilizers have found extensive use in the photostabilization ofpolyolefins. Prior to the present invention, the results obtained withthe known hindered amine light stabilizers have not been fullysatisfactory with all types of maunfactured articles, either from astabilization, compatibility, volatility, extrudability or economicviewpoint or combinations thereof. Therefore, further improvement in thefield of hindered amine light stabilizers is still desirable. The novelcompounds of this invention address these shortcomings.

Hydrazides have been used to prevent deterioration of polyolefins byheat, oxidation or heavy metal contamination. Derivatives of hydrazidesare also commercially available for use as polymer stabilizers. (SeeEncyclopedia of Polymer Science and Engineering, 2nd Ed. Vol. 2, pp83-84).

DEFINITIONS

As used herein, the term "acyl" refers to a substituent derived from acarboxylic acid group by removing the OH of the carboxyl group therebyproviding a free valence, i.e. the acyl group derived from a generalizedcarboxylic acid D--C(═O)--OH would have the formula D--C(═O)-- and wouldbe referred to herein as a "D acyl" group.

As used herein, the terms "polymer" and "polymeric composition(s)"include homopolymers or any type of copolymers.

When any generalized functional group or index such as R¹, R², a, b,etc., appears more than once in a general formula, their meanings areindependent of one another.

SUMMARY OF THE INVENTION

This invention is directed to compounds of formula I ##STR2## where

R¹ is hydrogen, oxyl, hydroxyl, substituted or unsubstituted aliphaticof 1-20 carbons, substituted or unsubstituted alicyclic of 5-12 carbons,substituted or unsubstituted araliphatic of 7-22 carbons, substituted orunsubstituted aliphatic acyl of 2-20 carbons, substituted orunsubstituted alicyclic acyl of 7-16 carbons, substituted orunsubstituted aromatic acyl of 7-11 carbons, substituted orunsubstituted araliphatic acyl of 7-22 carbons, --(C(═O))_(a)--N(R⁴)(R⁵), --(C(═O))_(a) --O--R⁶, --(CH₂)_(a) --C(═O)--O--R⁷ where ais 1-2, or --(CH₂ --CH(R⁸)--O)_(b) --R⁹ where b is 2-50. Preferably R¹is hydrogen, substituted or unsubstituted aliphatic of 1-4 carbons,substituted or unsubstituted araliphatic of 7-10 carbons, substituted orunsubstituted aliphatic acyl of 2-6 carbons or substituted orunsubstituted benzoyl. Most preferably R¹ is hydrogen, methyl, acetyl orbenzoyl.

R² is hydrogen or aliphatic of 1-4 carbons. Preferably R² is hydrogen ormethyl. Most preferably R² is hydrogen.

R³ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted araliphatic of 7-22 carbons or substitutedor unsubstituted alicyclic of 5-12 carbons. Preferably R³ is hydrogen.

R⁴ and R⁵ are independently hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted aryl of 6-14carbons, substituted or unsubstituted araliphatic of 7-22 carbons orsubstituted or unsubstituted alicyclic of 5-12 carbons which mayoptionally contain --N(R¹⁰)-- as a ring member and optionally R⁴ and R⁵may be linked together through a heteroatom --N(R¹⁰)-- or --O-- to forma heterocyclic ring of 5-7 atoms. Preferrably R⁴ and R⁵ areindependently hydrogen, substituted or unsubstituted aliphatic of 1-8carbons, substituted or unsubstituted phenyl or substituted orunsubstituted benzyl. Most preferably R⁴ is hydrogen, methyl or ethyl.Most preferably R⁵ is substituted or unsubstituted aliphatic of 1-8carbons, or substituted or unsubstituted phenyl.

R⁶ is substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons or substituted or unsubstitutedaraliphatic of 7-22 carbons. Preferably R⁶ is substituted orunsubstituted aliphatic of 1-8 carbons, substituted or unsubstitutedphenyl or substituted or unsubstituted benzyl.

R⁷, R⁸ and R⁹ are independently hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons orsubstituted or unsubstituted araliphatic of 7-22 carbons. Preferably R⁷,R⁸ and R⁹ are independently hydrogen, substituted or unsubstitutedaliphatic of 1-8 carbons, substituted or unsubstituted phenyl orsubstituted or unsubstituted benzyl.

R¹⁰ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted araliphatic of 7-22 carbons, substituted or unsubstitutedaliphatic acyl of 2-20 carbons, substituted or unsubstituted alicyclicacyl of 7-16 carbons, substituted or unsubstituted aromatic acyl of 7-11carbons substituted or unsubstituted araliphatic acyl of 7-22 carbons,--(C(═O))_(a) --N(R⁴)(R⁵), --(C(═O))_(a) --O--R⁶, --(CH₂)_(a)--C(═O)--O--R⁷ where a is 1-2, or --(CH₂ --CH(R⁸)--O)_(b) --R⁹ where bis 2-50. Preferably R¹⁰ is hydrogen, substituted or unsubstitutedaliphatic of 1-4 carbons, substituted or unsubstituted araliphatic of7-10 carbons, substituted or unsubstituted aliphatic acyl of 2-6 carbonsor substituted or unsubstituted benzoyl. Most preferably R¹⁰ ishydrogen, methyl, acetyl or benzoyl.

X is a triradical ##STR3##

R¹¹ is independently of the same definition as R⁷ and when alicyclic mayoptionally contain --N(R¹⁰)-- as a ring member.

R¹² is substituted or unsubstituted aliphatic diradical of 1-20 carbons,substituted or unsubstituted aryl diradical of 6-12 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons or substituted andunsubstituted araliphatic diradical of 7-22 carbons. The diradicals mayoptionally contain 1-6 heteroatoms --O--, --S--, and --N(R¹⁰)-- with theproviso that multiple heteroatoms must be separated from each other byat least two carbon atoms and from the diradical ends by at least onecarbon atom.

R¹³ is independently of the same definition as R⁶.

R¹⁴ is independently of the same definition as R¹². When Y is a directbond, R¹⁴ may also be a direct bond.

R¹³ and R¹⁴ together with the carbon atom linking them may form asubstituted or unsubstituted cycloalkyl ring of 5-12 carbons.

R¹⁵ and R¹⁶ are independently of the same definition as R¹¹ and may alsobe carbamoyl, alkoxycarbonyl of 2-5 carbons or pyridyl. R¹⁵ and R¹⁶ maybe linked together to form an alicyclic of 5-12 carbons, or may belinked together through a heteroatom --O--, --S--, and --N(R¹⁰)-- toform a heterocycle of 5-7 atoms. Preferably R¹⁵ and R¹⁶ areindependently substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-6 carbons, substituted orunsubstituted aryl of 6-10 carbons, substituted or unsubstitutedaraliphatic of 7-16 carbons, or may be linked together to form analicyclic of 5-12 carbons or may be linked together to form a group offormula ##STR4##

Y is --O--, --N(R¹¹)-- or a direct bond.

n is 1 or 2.

When n is 1, Z is ##STR5##

R¹⁷ is independently of the same definition as R¹¹. Preferably R¹⁷ ishydrogen, substituted or unsubstituted aliphatic of 1-12 carbons,substituted or unsubstituted alicyclic of 5-8 carbons, substituted orunsubstituted phenyl or substituted or unsubstituted araliphatic of 7-9carbons. Most preferably R¹⁷ is hydrogen, substituted or unsubstitutedaliphatic of 1-10 carbons, substituted or unsubstituted cyclohexyl,substituted or unsubstituted phenyl or substituted or unsubstitutedaraliphatic of 7-14 carbons.

R¹⁸ is independently of the same definition as R¹¹. Preferably R¹⁸ isselected from hydrogen, substituted or unsubstituted aliphatic of 1-12carbons, substituted or unsubstituted alicyclic of 5-8 carbons,substituted or unsubstituted phenyl or substituted or unsubstitutedaraliphatic of 7-9 carbons and when alicyclic R¹⁸ may optionally contain1-2 heteroatoms selected from --O-- and --N(R¹⁰)-- with the provisostated above. Most preferably R¹⁸ is selected from hydrogen, substitutedor unsubstituted aliphatic of 1-10 carbons, substituted or unsubstitutedcyclohexyl, substituted or unsubstituted phenyl or substituted orunsubstituted araliphatic of 7-14 carbons and when alicyclic R¹⁸ may besubstituted piperidin-4-yl.

Q is --C(═O)--, --S(═O)₂ --, --C(═O)--O--, --[C(═O)]₂ --O--,--C(═O)--N(R¹⁰)--, --[C(═O)]₂ --N(R¹⁰)--, --C(═S)--N(R¹⁰)--, --C(═O)-R²²--C(═O)--N(R¹⁰)--, or, when n is 1, a direct b between the nitrogen andR¹⁸. Preferably Q is --C(═O)--, --C(═O)--O--, --[C(═O)]₂ --O--,--C(═O)--N(R¹⁰)--, --C(═O)₂ --N(R¹⁰)-- or, when n is 1, a direct bondbetween the nitrogen and R¹⁸.

R¹⁹ and R²⁰ are independently of the same definition as R¹¹, R¹⁹ and R²⁰may be linked together to form a substituted or unsubstituted alicyclicring of 5-12 carbons or may can be linked together through a heteroatom--N(R¹⁰)--, --O-- and --S-- to form a heterocyclic ring of 5-12 atoms.Preferably R¹⁹ and R²⁰ are independently substituted or unsubstitutedaliphatic of 1-8 carbons, substituted or unsubstituted alicyclic of 5-8carbons, substituted or unsubstituted aryl of 6-12 carbons orsubstituted or unsubstituted araliphatic of 7-14 carbons, and R¹⁹ andR²⁰ may be linked together to form a substituted or unsubstitutedcycloalkyl ring of 5-8 carbons or a group of formula ##STR6##

R²¹ is substituted or unsubstituted aliphatic diradical of 2-200carbons, substituted or unsubstituted aryl diradical of 6-14 carbons,substituted or unsubstituted alicyclic diradical of 5-12 carbons orsubstituted or unsubstituted araliphatic diradical of 7-22 carbons. Thediradical chain(s) may optionally contain 1-6 heteroatoms --O--, --S--and --N(R¹⁰)-- with the provisos that (a) multiple heteroatoms must beseparated from each other by at least two carbon atoms and from thechain ends by at least one carbon atom, and that (b) the cyclic groupformed contains 5-6 atoms in the ring. Preferably R²¹ is substituted orunsubstituted aliphatic diradical of 2-18 carbons, substituted orunsubstituted ortho-phenylene or substituted or unsubstituted alicyclicdiradical of 6-8carbons. The diradical chain(s) may optionally contain1-2 heteroatoms --O-- and --N(R¹⁰)-- with the provisos stated above.

R²² is a direct bond or is substituted or unsubstituted aliphaticdiradical of 1-200 carbons, substituted or unsubstituted aryl diradicalof 6-14 carbons, substituted or unsubstituted alicyclic diradical of5-12 carbons or substituted or unsubstituted araliphatic diradical of7-22 carbons. The diradical chain(s) may optionally contain 1-6heteroatoms --O--, --S--, and --N(R¹⁰)-- with the proviso that multipleheteroatoms must be separated from each other by at least two carbonatoms and from the chain ends by at least one carbon atom. PreferablyR²² is substituted or unsubstituted aliphatic diradical of 2-18 carbons,substituted or unsubstituted phenylene or substituted or unsubstitutedalicyclic diradical of 6-8 carbons. The diradical chain(s) mayoptionally contain 1-2 heteroatoms --O-- and --N(R¹⁰)-- with the provisostated above.

R²³ is independently of the same definition as R¹¹. Preferably R²³ ishydrogen, substituted or unsubstituted aliphatic of 1-8 carbons,substituted or unsubstituted araliphatic of 7-8 carbons or substitutedor unsubstituted alicyclic of 5-8 carbons.

R²⁴ is chosen from --NH(R¹⁸), --OH and O⁻ M⁺, where M is sodium ion,potassium ion or ammonium ion. Preferably R²⁴ is --OH or --O⁻ M⁺ where Mis sodium ion. Most preferably R²⁴ is --OH.

R²⁵ is substituted or unsubstituted aliphatic diradical of 1-20 carbons,substituted or unsubstituted aryl diradical of 6-12 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons or substituted orunsubstituted araliphatic diradical of 7-22 carbons. The diradicalchain(s) may optionally contain 1-6heteroatoms selected from --O-- and--N(R¹⁰)-- with the proviso that multiple heteroatoms must be separatedfrom each other by at least two carbon atoms and from the chain ends byat least one carbon atom. Preferably R²⁵ is substituted or unsubstitutedaliphatic diradical of 2-12 carbons, substituted or unsubstituted aryldiradical of 6-12 carbons, substituted or unsubstituted alicyclicdiradical of 5-12 carbons or substituted or unsubstituted araliphaticdiradical of 7-12 carbons. The diradical chain(s) may optionally contain1-2 heteroatoms selected from --O-- and --N(R¹⁰)-- with the provisostated above. Most preferably R²⁵ is substituted or unsubstitutedaliphatic diradical of 2-10 carbons, substituted or unsubstitutedphenylene, substituted or unsubstituted alicyclic diradical of 5-8carbons or substituted or unsubstituted araliphatic diradical of 7-12carbons.

Optional substituents for R¹, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ and R²⁵ are one ormore of the following: chloro, bromo, alkyl of 1-8 carbons, alkoxy of1-12 carbons, phenoxy, cyano, hydroxy, epoxy, carboxy, benzoyl,benzoyloxy, dialkylamino of 2-8 carbons total, alkyoxycarbonyl of 2-6carbons, acyloxy of 1-4 carbons, acryloyl, acryloyloxy, methacryloyl,methacryloyloxy, hydroxymethyl, hydroxyethyl, alkylthio of 1-4 carbonsand trialkoxysilyl of 3-12 carbons. Additional optional substituents forR²¹ and R²² are alkyl of 5-180 carbons, alkylthio of 5-180 carbons,aralkylthio of 7-20 carbons, arylthio of 6-20 carbons, alkenyl of 2-180carbons, cycloalkenyl of 5-12 carbons, aryl of 6-16 carbons, aralkyl of7-17 carbons, aryloxy of 6-16 carbons, alkoxycarbonyl of 7-10 carbons,and (alkoxycarbonyl)alkylthio of 3-30 carbons. Additional substituentsfor R¹⁸ are chosen from aliphatic of 1-20 carbons, cycloaliphatic of5-12 carbons, aryl of 6-14 carbons, aralkyl of 7-22 carbons, alkoxy of1-20 carbons, cycloalkoxy of 5-12 carbons, aryloxy of 6-14 carbons,aralkoxy of 7-15 carbons, aliphatic acyloxy of 2-20 carbons, alicyclicacyloxy of 6-13 carbons, aromatic acyloxy of 7-15 carbons, andaraliphatic acyloxy of 8-16 carbons.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Generic Group Examples

As a substituted or unsubstituted aliphatic of 1-20 carbons, R¹, R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²³are, for example, methyl, ethyl, n-propyl, isopropyl, butyl, allyl,hexyl, heptyl, octyl, nonyl, decyl, propargyl, octadecyl, dodecyl,isododecyl, tetradecyl, 2-methallyl, 2-hexenyl, 10-undecenyl,2-dodecenyl, n-butyl, 2-hydroxyethyl, 2-butenyl, 2-hydroxyhexadecyl,2-hydroxypropyl, 2-hexenyl, 10-undecenyl, 2-dodecenyl, 2-hydroxydodecyl,2-hydroxy-5-hexenyl, 2-hydroxyhexyl, 2-hydroxydecyl, 2-hydroxyoctadecyl,2-hydroxy-3-(methacryloyloxy)propyl, 2-hydroxy-3-(acryloyloxy)propyl,2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-(4-methoxyphenoxy)propyl,2-hydroxy-3-isopropoxypropyl, 2-hydroxy-3.-methoxypropyl,2-hydroxy-3-(2-ethylhexyloxy)propyl, 2-hydroxy-3-(cyclohexyloxy)propyl,2-hydroxy-3-(benzyloxy)propyl, 2-hydroxy-3-(benzoyloxy)propyl,2-hydroxy-3-dodecyloxypropyl, 2-hydroxybutyl, 1-methyl-2-hydroxypropyl,cyanomethyl, 2,3-epoxypropyl or 2-(dimethylamino)ethyl.

As a substituted or unsubstituted alicyclic of 5-12 carbons, R¹, R³, R⁴,R⁵, R⁶, R⁷, R⁸ R⁹, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²³are, for example, cyclohexyl, trimethylcyclohexyl, cyclooctyl,cyclododecyl, 4-t-butylcyclohexyl, 2-hydroxycyclododecyl,3-cyclohexenyl, 2-hydroxycyclohexyl, 2-hydroycyclopentyl, cyclododecyl,4-octylcyclohexyl or 2-methyl-4-octylcyclohexyl.

As substituted or unsubstituted aryl of 6-14 carbons R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹¹, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²³ are, for example,phenyl, tolyl, 4-chlorophenyl, isopropylphenyl, isopropenylphenyl,anisyl, 3,5-di(t-butyl)-4-hydroxyphenyl, 3,5-di(t-amyl)-4-hydroxyphenyl,3-(t-butyl)-5-methyl-4-hydroxyphenyl, naphthyl,3-methyl-5-t-butyl-4-hydroxyphenyl, 3,4,5-trimethoxyphenyl or4-(dimethylamino)phenyl.

As a substituted of unsubstituted araliphatic group of 7-22 carbons, R¹,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰and R²³ are, for example, benzyl, 3-methylbenzyl, 4-t-butylbenzyl,cinnamyl, 3,5-di-t-butyl-4-hydroxybenzyl, 2-hydroxy-2-phenylethyl,2-phenylethyl, cumyl, trimethylbenzyl, 4-octyloxybenzyl, naphthylmethyl,or (4-dodecylphenyl)methyl, 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl,2-(3,5-di-t-amyl-4-hydroxyphenyl)ethyl or2-(3-t-butyl-5-methyl-4-hydroxyphenyl)ethyl.

As a substituted or unsubstituted aliphatic acyl of 2-20 carbons,substituted or unsubstituted alicyclic acyl of 7-16 carbons, substitutedor unsubstituted aromatic acyl of 7-11 carbons, or substituted orunsubstituted araliphatic acyl of 7-22 carbons, R¹ and R¹⁰ are, forexample, formyl, acetyl, chloroacetyl, acryloyl, methacryloyl,propionyl, butyryl, 2-methylpropionyl, caproyl, capryloyl, lauroyl,crotonoyl, stearoyl, octadecanoyl, cyclohexylcarbonyl,4-t-butylcyclohexylcarbonyl, 3-cyclohexenyl-1-carbonyl,cyclododecylcarbonyl, 4-octylcyclohexylcarbonyl, 2-ethoxy-2-oxoacetyl,2-methoxy-2-oxoacetyl, 2-methyl-4-octylcyclohexylcarbonyl, benzoyl,toluoyl, 4-chlorobenzoyl, isopropylbenzoyl, anisoyl, hydroxybenzoyl,3,5-di™t-butyl-4-hydroxybenzoyl, naphthoyl,3-methyl-5-t-butyl-4-hydroxybenzoyl, 3,4,5-trimethoxybenzoyl,4-dimethylaminobenzoyl, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl,cinnamoyl or dihydrocinnamoyl; preferably alkanoyl of 2-5 carbons,cyclohexylcarbonyl, benzoyl or phenacyl.

As --(C(═O))_(a) --N(R⁵)(R⁴) wherein optionally R⁴ and R⁵ may be linkedtogether through a heteroatom --N(R¹⁰)-- or --O-- to form a heterocylicring of 5-7atoms, R¹ and R¹⁰ are, for example, N-methylcarbamoyl,N-butylcarbamoyl, N-octadecylcarbamoyl, N-dodecylcarbamoyl,N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N-cyclohexylcarbamoyl,N,N-dihexylcarbamoyl, piperidin-1-ylcarbonyl,2,2,6,6-tetramethyl-4-piperidinylcarbonyl, piperazine-1-carbonyl,4-methylpiperazine-1-carbonyl, morpholin-1-carbonyl,2-(dibutylamino)-2-oxoacetyl, 2-(phenylamino)-2-oxoacetyl,N-phenylcarbamoyl, N-benzylcarbamoyl, N-(4-butylphenyl)carbamoyl,N-(alpha-naphthyl)carbamoyl, N-phenyl-N-hexylcarbamoyl,N-(trimethylphenyl)-N-amylcarbamoyl, N,N-diphenylcarbamoyl,N,N-di-(4-methylphenyl)carbamoyl orN-(4-benzylaminophenyl)-N-phenylcarbamoyl.

As --(C(═O))_(a) --O--R⁶, R¹ and R¹⁰ are, for example, methoxycarbonyl,2-ethoxy-2-oxoacetyl, 2-methoxy-2-oxoacetyl,2-cyclohexyloxy-2-oxoacetyl, 2-octadecyloxy-2-oxoacetyl, ethoxycarbonyl,phenoxycarbonyl, methallyloxycarbonyl, (2-methylphenoxy)carbonyl,allyloxycarbonyl, cyclopentoxycarbonyl, cyclohexoxycarbonyl,cyclododecyloxycarbonyl, (2-ethylhexyl)oxycarbonyl, ethoxycarbonyl,isopropoxycarbonyl or (4-octyloxyphenyl)carbonyl.

As --(CH₂)_(a) --C(═O)--O--R⁷, R¹ and R¹⁰ are, for example,methoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, butoxycarbonylmethyl,(benzyloxy)carbonylmethyl or 2-(benzyloxycarbonyl)ethyl.

As --(CH₂ --CH(R⁸)--O)_(b) --R⁹, R¹ and R¹⁰ are, for example,nonylphenoxypoly(ethoxy)ethyl, butoxypoly(propoxy)ethyl,benzyloxypoly(ethoxy)ethyl, hydroxypoly(ethoxy)ethyl or2-[hydroxypoly(propoxy)]-2-methylethyl.

As an aliphatic group of 1 to 4 carbons, R² is, for example, methyl,ethyl, propyl, isopropyl, butyl, sec-butyl or t-butyl.

As a substituted or unsubstituted aliphatic diradical of 1-20 carbon,substituted or unsubstituted aryl diradical of 6-12 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons and substituted orunsubstituted araliphatic diradical of 7-22 carbons, said diradicalscontaining 1-6 heteroatoms --O--, --S--, and --N(R¹⁰)--, R¹² and R¹⁴are, for example, 1,2-ethanediyl, methylene, 1,2-propenediyl,1-phenyl-1,2-ethanediyl, 1,3-hexanediyl, 1,4-butanediyl,1,2-cyclohexanediyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene,4-methyl-4-cyclohexene-1,2-diyl, 4-cyclohexene-1,2-diyl,4-methylcyclohexane-1,2-diyl, propane-2,2-bis[4-cyclohexyl],3-oxapentane-1,5-diyl, methylenebis[4-cyclohexyl],1,2-phenylenebis(methyl), 1,3-phenylenebis(methyl),1,4-phenylenebis(methyl), biphenyl-4,4'-diyl, biphenyl-3,3'-diyl,biphenyl-3,4'-diyl, methylenebis[phenylene], 1,2-propanediyl,1,3-propanediyl, 1,4-butanediyl, 1,18-octadecanediyl,2,2-dimethyl-1,3-propanediyl, 2-methylpentane-2,4-diyl, 1,10-decanediyl,1,12-dodecanediyl, 3-oxapentane-1,5-diyl, 4-oxaheptane-1,7-diyl,3,6-dioxaoctane-1,8-diyl, 4,9-dioxadodecane-1,12-diyl,4-methyl-4-azaheptane-1,4-diyl, 3,6-diaza-3,6-dimethyl-1,8-octanediyl,3-methyl-3-azapentane-1,5-diyl, 1,2-cyclohexanediyl or1,4-cyclohexanediyl.

When linked together with the carbon atom linking them forming acycloalkyl ring of 5-12 carbons, R¹³ and R¹⁴ form, for example,cyclopentyl, cyclohexyl, cycloheptyl, t-butylcyclohexyl,methylcyclohexyl, cyclooctyl, and cyclododecyl.

When alkoxycarbonyl of 2-5 carbons, R¹⁵ and R¹⁶ are, for example,methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl and butoxycarbonyl.

When taken together with the carbon to which they are attached can forma substituted or unsubstituted saturated alicyclic group of 5-12 carbonsor linked together through a heteroatom --O--, --S-- and --N(R¹⁰)-- toform a heterocycle of 5-7 atoms, R¹⁵ and R¹⁶ are, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl,4-oxacyclohexyl, 3,5-dimethylcyclohexyl, 4-thiacyclohexyl,2,2,6,6-tetramethyl-4-piperidinyl, 3,3,5-trimethylcyclohexyl,3-methoxycyclohexyl, 4-t-butylcyclohexyl, cycloundecyl and3,3,5,5-tetramethylcyclohexyl.

When alicyclic and optionally containing --N(R¹⁰)-- as a ring member,R⁴, R⁵, R¹¹, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²³ are, for example,2,2,6,6-tetramethyl-4-piperidinyl,2,6-diethyl-1,2,3,6-tetramethyl-4-piperidinyl,1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl and1-(4-methylbenzoyl)-2,6-dimethyl-2,6-dipropyl-3-ethyl-4-piperidinyl.

When linked together to form a substituted or unsubstituted alicyclic of5-12 carbons, or when linked together by --N(R¹⁰)--, --O-- or --S--, R¹⁹and R²⁰ form, for example, cyclopentyl, cyclohexyl, cycloheptyl,4-t-butylcyclohexyl, 2-methylcyclohexyl, cyclooctyl,2,2,6,6-tetramethyl-4-piperidinyl,2,6-diethyl-2,3,6-trimethyl-4-piperidinyl,1,2,2,6,6-pentamethyl-4-piperidinyl,1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl,1-ethyl-2,2,6,6-tetramethyl-4-piperidinyl, 4-oxacyclohexyl, and4-thiacyclohexyl.

As a substituted or unsubstituted aliphatic diradical of 2-200 carbons,substituted or unsubstituted aryl diradical of 6-14 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons, or substituted orunsubstituted araliphatic diradical of 7-22 carbons, any of which mayoptionally contain 1-6 heteroatoms selected from --O--, --S--, and--N(R¹⁰)-- with the provisos that (a) multiple heteroatoms must beseparated from each other by at least two carbon atoms and from thechain ends by at least one carbon atom and that (b) the cyclic groupformed contains 5-6 atoms in the ring, R²¹ is, for example,1,2-ethanediyl, 1,2-ethenediyl, 1,3-propanediyl, 1,2-propenediyl,2-thiapropane-1,3-diyl, 2-oxapropane-1,3-diyl, 1-chloro-1,2-ethenediyl,1-phenyl-1,2-ethenediyl, 1,3-hexanediyl, 2-azapropane-1,3-diyl,2-methyl-2-azapropane-1,3-diyl, 1,2-cyclohexanediyl, 1,2-phenylene,4-methyl-4-cyclohexene-1,2-diyl, 4-cyclohexene-1,2-diyl,4-methylcyclohexane-1,2-diyl, norbornane-2,3-diyl,5-norbornene-2,3-diyl, bicyclo[2.2.2]octane-2,3-diyl,bicyclo[2.2.2]oct-5-ene-2,3-diyl, bicyclo[2.2.1]heptane-1,2-diyl,bicyclo[2.2.1]heptane-1,2-diyl, 4-carboxy-1,2-phenylene,4-methoxycarbonyl-1,2-phenylene, 1-(substituted)ethane-1,2-diyl whereinthe substituent is chosen from hydrogen, chloro, phenyl, methyl, ethyl,propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl,hexenyl, isohexenyl, diisobutenyl, decenyl, dodecenyl, isododecenyl,octenyl, nonenyl, tetradecenyl, hexadecenyl, octadecenyl,isooctadecenyl, triacontenyl, and polyisobutenyl;1-(substituted)ethane-1,2-diyl, 5-(substituted)norbornane-2,3-diyl,5-(substituted)bicyclo[2.2.2]octane-2,3-diyl, and4-(substituted)cyclohexane-1,2-diyl wherein the substituent is chosenfrom methylthio, ethylthio, butylthio, hexylthio, octylthio,hexadecylthio, octadecylthio, 2-hydroxyethylthio, phenylthio,benzylthio, (3,5-di-t-butyl-4-hydroxy)phenylthio, and(3-t-butyl-5-methyl-4-hydroxyphenyl)benzylthio.

As a substituted or unsubstituted aliphatic diradical of 1-200 carbons,substituted or unsubstituted aryl diradical of 6-14 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons, or substituted orunsubstituted araliphatic diradical of 7-22 carbons, any of which mayoptionally contain 1-6 heteroatoms selected from --O--, --S--, and--N(R¹⁰)-- with the proviso that multiple heteroatoms must be separatedfrom each other by at least two carbon atoms and from the chain ends byat least one carbon atom, R²² is, for example, methylene,1,2-ethanediyl, 1,2-ethenediyl, 1,3-propanediyl, 1,2-propenediyl,2-thiapropane-1,3-diyl, 3-thiapentane-1,2-diyl, 2-oxapropane-1,3-diyl,1-chloro-1,2-ethenediyl, 1-phenyl-1,2-ethenediyl, 1,3-hexanediyl,2-azapropane-1,3-diyl, 2-methyl-2-azapropane-1,3-diyl,1,2-cyclohexanediyl, 1,2-phenylene, 4-methyl-4-cyclohexene-1,2-diyl,4-cyclohexene-1,2-diyl, 4-methylcyclohexane-1,2-diyl,norbornane-2,3-diyl, 5-norbornene-2,3-diyl,bicyclo[2.2.2]octane-2,3-diyl, bicyclo[2.2.2]oct-5-ene-2,3-diyl,bicyclo[2.2.1]heptane-1,2-diyl, bicyclo[ 2.2.1]heptane-1,2-diyl,4-carboxy-1,2-phenylene, 4-methoxycarbonyl-1,2-phenylene,propane-2,2-bis4-cyclohexyl], 3-oxapentane-1,5-diyl,methylenebis[4-cyclohexyl], 1,2-, 1,3-, or 1,4-phenylene, 1,2-, 1,3-, or1,4-phenylenebis(methyl), or 2,5-diazahexane-1,6-diyl;biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, biphenyl-3,4'-diyl,methylenebis[phenylene], 1-(substituted)ethane-1,2-diyl wherein thesubstituent is chosen from hydrogen, chloro, phenyl, methyl, ethyl,propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl,hexenyl, isohexenyl, diisobutenyl, decenyl, dodecenyl, isododecenyl,octenyl, nonenyl, tetradecenyl, hexadecenyl, octadecenyl,isooctadecenyl, triacontenyl, and polyisobutenyl;1-(substituted)ethane-1,2-diyl, 5-(substituted)norbornane-2,3-diyl,5-(substituted)bicyclo[2.2.2]octane-2,3-diyl, and4-(substituted)cyclohexane-1,2-diyl wherein the substituent is chosenfrom methylthio, ethylthio, butylthio, hexylthio, octylthio,hexadecylthio, octadecylthio, 2-hydroxyethylthio, phenylthio,benzylthio, (3,5-di-t-butyl-4-hydroxy)phenylthio, and(3-t-butyl-5-methyl-4-hydroxyphenyl)benzylthio.

As a substituted or unsubstituted aliphatic diradical of 1-20 carbons,substituted or unsubstituted aryl diradical of 6-12 carbons, substitutedor unsubstituted alicyclic diradical of 5-12 carbons, or substituted orunsubstituted araliphatic diradical of 7-22 carbons, the diradicalchain(s) optionally contain 1-6 heteroatoms selected from --O--, --S--,and --N(R¹⁰)-- with the proviso that multiple heteroatoms must beseparated from each other by at least two carbon atoms and from thechain ends by at least one carbon atom, R²⁵ is, for example, methylene,ethane-1,2-diyl, ethene-1,2-diyl, propane-1,3-diyl, propene-1,2-diyl,2-thiapropane-1,3-diyl, 2-oxapropane-1,3-diyl, hexane-1,3-diyl,2-azapropane-1,3-diyl, 2-methyl-2-aza-propane-1,3-diyl,cyclohexane-1,2-diyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene,hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl, dodecane-1,12-diyl,3-hexene-1,6-diyl, 4-methyl-1,2-phenylene, 4-chloro-1,2-phenylene,4-methylcyclohexane-1,2-diyl, cyclohexane-1,2-diyl,4-methyl-4-cyclohexene-1,2-diyl, toluene-alpha,2-diyl,toluene-alpha,3-diyl, toluene-alpha,4-diyl,3,3'-dimethoxybiphenyl-4,4'-diyl, 3,3'-dimethylbiphenyl-4,4'-diyl,methylenebis(4-phenyl), methylenebis(4-cyclohexyl) and isophoronediyl.

EXAMPLES OF COMPOUNDS

Examples of the hindered amine light stabilizers of this inventioninclude the following non-limiting list:

1.3-acetyl-2,2,4,4-tetramethyl-20-[4,5,7-triaza-3-oxo-6-(thiooxo)undecyl]-7-oxa-3,20-diazadispiro[5.1.11.-2]-heneicosan-21-one

2.2,4-diethyl-1,2,3,4-tetramethyl-14-{2-[N-(n-hexadecylsuccinimidyl)amino]-2-oxoethyl}-7-oxa-3,1-4-diazadispiro[5.1.5.2]pentadecan-15-one

3.14,14'-(4,5,7,14,16,17-hexaaza-3,6,15,18-tetraoxaeicosane-1,20-diyl}bis{2,2,4,4,-tetramethyl-7-oxa-3,14-diazadispiro[5.1.4.2]tetradecane-13-one}

4.8-allyl-7,7,9,9-tetramethyl-1,3,8-triaza-3-[4-hydrazino-4-oxobutyl]spiro[4.5]decane-2,4-dione

5.2,2,4,4-tetramethyl-14-(4,5,7-triaza-3,6-dioxopentacosanyl}-7-oxa-3,14-diazatrispiro[5.1.11.2]heneicosane-21-one

6.8-(2-acetoxyethyl)-2,7,7,9,9-pentamethyl-2-(4,5-diaza-3,6-dioxoheptyl)-3,8-diaza-1-oxaspiro[4.5]decane-4-one

7.2,8-dibutyl-4,7,7,9,9-pentamethyl-2-[2-hydrazino-2-oxoethyl]-1-oxa-3,8-diazaspiro[4.5]decane-3-one,hydrazone of 2,2,6,6-tetramethyl-4-piperidone

8.2,2,4,4-tetramethyl-20-[6,6-dimethyl-4,5-diaza-3-oxoheptyl]-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

9.2,2,4,4-tetramethyl-20-{3-[N-(maleimido)amino]-3-oxopropyl}-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

10.2,2,4,4-tetramethyl-20-[3-hydrazino-3-oxopropyl]-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one,hydrazone of 2-pentanone

11.1-benzyl-2,2,4,4-tetramethyl-20-[4,5-diaza-8-oxo-3,6-dioxa-9-carboxynonyl]-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

12.2,2-dipropyl-3-[4,5-diaza-3,6-dioxo-7-oxatridecyl]-6-phenyl-7,8-dimethyl-7,8-dibenzyl-1-oxa-3,8-diazaspiro[4.5]decane-4-one

13.2,2,4,4-tetramethyl-20-[4,5,8-triaza-3,6,7-trioxo-8-di(2,2,6,6-teteamethyl-4-piperidinyl)octyl]7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one

14.9,9'-[diphenylmethane-4,4'-diylbis(1,3,4-triaza-2,5-dioxohex-6-yl]bis{7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione}

15.1,7,7,8,9,9-hexamethyl-3-[5-methyl-8-carboxy-4,5-diaza-3,6-dioxooctyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione,sodium salt

16.2,2,4,4-tetramethyl-3-[(4-methoxyphenyl)methoxy-carbonyl]-20-[8-(4-methoxyphenyl)-4,5-diaza-7-oxa-3,6-dioxooctyl]-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

17.2,2,4,4-tetramethyl-20-{3-[(tetrahydro-4-methylphthalimido)amino]-3-oxopropyl}-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

18.2,2,4,4-tetramethyl-3-(2-hydroxyoctadecyl)-20-[7-(2-hydroxyoctadecyl)-7-hydroxy-4,5-diaza-3-oxotricosanyl]-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

19.2,7,7,9,9-pentamethyl-2-phenyl-8-(2-hydroxypropyl)-4-[6-hydroxy-2-oxo-4-(2-hydroxypropyl)-3,4-diazaheptyl]-1-oxa-4,8-diazaspiro[4.5]decane-3-one

20.7,7,8,9,9-pentamethyl-3-[7-(4-(ethoxycarbonyl)phthalimido)-3-thia-7-aza-6-oxoheptyl]-1-oxa-3,8-diazadispiro[5.1.11.2]heneicosane-4-one

Utility

The novel stabilizers of this invention are very effective additives forthe stabilization of polymeric compositions which are normally subjectto thermal, oxidative or actinic light degradation. At times it may bebeneficial to add extraneous additives which will act as synergists withthe hindered amine light stabilizing groups.

The novel stabilizers of this invention can be blended with variouspolymeric compositions in high concentrations to form masterbatcheswhich can then be blended with additional polymer either of the same ordifferent type.

The amount of stabilizer used to stabilize the polymeric compositionwill depend on the particular polymer system to be stabilized, thedegree of stabilization desired and the presence of other stabilizers inthe composition Normally it is advisable to have about 0.01 to about 5%by weight of the 2,2,6,6-tetraalkylpiperidine moiety present in thepolymeric composition. An advantageous range is from about 0.05 to about2% by weight of the 2,2,6,6-tetraalkylpiperidine portion of the moleculein the final composition. In most cases 0.1 to about 1% by weight issufficient.

The hindered amine light stabilizers of this invention are alsointermediates for the polymer bound hindered amine light stabilizersdisclosed and claimed in U.S. Pat. No. 4,857,595.

Examples of polymeric compositions which may be stabilized by thesenovel hindered amine light stabilizers include:

1. Polyolefins such as high, low and linear low density polyethylenes,which may be optionally crosslinked, polypropylene, polyisobutylene,poly(methylbutene-1), polyacetylene and in general polyolefins derivedfrom monomers having from two to about ten carbon atoms and mixturesthereof.

2. Polyolefins derived from diolefins such as polybutadiene andpolyisoprene.

3. Copolymers of mono or diolefins such as ethylene-propylene,propylene-butene-1, propylene-isobutylene and ethylene-butene-1copolymer.

4. Terpolymers of ethylene and propylene with dienes (EPDM) such asbutadiene, hexadiene, dicyclopentadiene and ethylidene norbornene.

5. Copolymers of alpha-olefins with acrylic acid or methacrylic acids ortheir derivatives such as ethylene-acrylic acid, ethylene-methacrylicacid and ethylene-ethyl acrylate copolymers.

6. Styrenic polymers such as polystyrene (PS) and poly(p-methylstyrene).

7. Styrenic copolymers and terpolymers such as styrene-butadiene (SBR),styrene-allyl alcohol and styrene-acrylonitrile (SAN),styrene-acrylonitrile-methacrylate terpolymer, styrene-butadiene-styreneblock copolymers (SBS), rubber modified styrenics such asstyrene-acrylonitrile copolymers modified with acrylic ester polymer(ASA), graft copolymers of styrene on rubbers such as polybutadiene(HIPS), polyisoprene or styrene-butadiene-styrene block copolymers(Stereon™ products available from Firestone Synthetic Rubber and LatexCo.), graft copolymers of styrene-acrylonitrile on rubbers such asbutadiene (ABS), polyisoprene or styrene-butadiene-styrene blockcopolymers, graft copolymers of styrene-methyl methacrylate on rubberssuch as polybutadiene (MBS), butadiene-styrene radial block copolymers(e.g. KRO 3 of Phillips Petroleum Co.), selectively hydrogenatedbutadiene-styrene block copolymers (e.g. Kraton G from Shell ChemicalCo.) and mixtures thereof.

8. Polymers and copolymers derived from halogen-containing vinylmonomers such as poly(vinyl chloride), poly(vinyl fluoride),poly(vinylidene chloride), poly(vinylidene fluoride),poly(tetrafluoroethylene) (PTFE), vinyl chloride-vinyl acetatecopolymers, vinylidene chloride-vinyl acetate copolymers andethylene-tetrafluoroethylene copolymers.

9. Halogenated rubbers such as chlorinated and/or brominated butylrubbers or polyolefins and fluoroelastomers.

10. Polymers and copolymers derived from alpha, beta-unsaturated acids,anhydrides, esters, amides and nitriles or combinations thereof such aspolymers or copolymers of acrylic and methacrylic acids, alkyl and/orglycidyl acrylates and methacrylates, acrylamide and methacrylamide,acrylonitrile, maleic anhydride, maleimide, the various anhydridecontaining polymers and copolymers described in this disclosure,copolymers of the above polymers and various blends and mixtures thereofas well as rubber modified versions of the above polymers andcopolymers.

11. Polymers and copolymers derived from unsaturated alcohols or theiracylated derivatives such as poly(vinyl alcohol), poly(vinyl acetate),poly(vinyl stearate), poly(vinyl benzoate), poly(vinyl maleate),poly(vinyl butyral), poly(allyl phthalate), poly(allyl diethylene glycolcarbonate) (ADC), ethylene-vinyl acetate copolymer and ethylene-vinylalcohol copolymers.

12. Polymers and copolymers derived from unsaturated amines such aspoly(allyl melamine).

13. Polymers and copolymers derived from epoxides such as polyethyleneoxide, polypropylene oxide and copolymers thereof as well as polymersderived from bis-glycidyl ethers.

14. Poly(phenylene oxides), poly(phenylene ethers) and modificationsthereof containing grafted polystyrene or rubbers as well as theirvarious blends with polystyrene, rubber modified polystyrenes or nylon.

15. Polycarbonates and especially the aromatic polycarbonates such asthose derived from phosgene and bisphenols such as bisphenol-A,tetrabromobisphenol-A and tetramethylbisphenol-A.

16. Polyester derived from dicarboxylic acids and diols and/orhydroxycarboxylic acids or their corresponding lactones such aspolyalkylene phthalates (e.g. polyethylene terephthalate (PET),polybutylene terephthalate (PBT), and poly(1,4-dimethylcyclohexaneterephthalate) or copolymers thereof) and polylactones such aspolycaprolactone.

17. Polyarylates derived from bisphenols (e.g. bisphenol-A) and variousaromatic acids such as isophthalic and terephthalic acids or mixturesthereof.

18. Aromatic copolyestercarbonates having carbonate as well as esterlinkages present in the backbone of the polymers such as those derivedfrom bisphenols, iso- and terephthaloyl chlorides and phosgene.

19. Polyurethanes and polyureas.

20. Polyacetals such as polyoxymethylenes and polyoxymethylenes whichcontain ethylene oxide as a comonomer.

21. Polysulfones, polyethersulfones and polyimidesulfones.

22. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams such as the following nylons: 6, 6/6, 6/10, 11 and12.

23. Polyimides, polyetherimides, polyamideimides and copolyetheresters.

24. Cross-linked polymers which are derived from aldehydes on the onehand and from phenols, ureas and melamine on the other hand such asphenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

25. Alkyd resins such as glycerol-phthalic acid resins and mixturesthereof with melamine-formaldehyde resins.

26. Blends of vinyl monomers and unsaturated polyester resins which arederived from copolyesters of saturated and unsaturated dicarboxylicacids with polyhydric alcohols as well as from vinyl compounds(crosslinking agents) and also halogen-containing, flame resistantmodifications thereof.

27. Natural polymers such as cellulose, natural rubber as well as thechemically modified homologous derivatives thereof such as celluloseacetates, cellulose propionate, cellulose butyrate and the celluloseethers such as methyl and ethyl cellulose.

In addition the novel stabilizers of this invention may be used tostabilize various combinations or blends of the above polymers orcopolymers. They are particularly useful in the stabilization ofpolyolefins, acrylic coatings, styrenics, rubber modified styrenics,poly(phenylene oxides) and their various blends with styrenics,rubber-modified styrenics or nylon.

The novel hindered amine light stabilizers of this invention can be usedtogether with other additives to further enhance the properties of thefinished polymer. Examples of other additives that can be used inconjunction with the stabilizers of this invention include antioxidantssuch as alkylated monophenols, alkylated hydroquinones, hydroxylatedthiodiphenyl ethers, alkylidene-bisphenols, hindered phenolic benzylcompounds, acylaminophenols, esters of3-(3,5-di-t-butyl-4-hydroxyphenyl)- propionic acid, esters of3-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid,3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid amides; UV absorbersand light stabilizers such as 2-(2'-hydroxyphenyl)-2H-benzotriazoles,2-hydroxybenzophenones, benzylidene malonate esters, esters ofsubstituted or unsubstituted benzoic acids, diphenyl acrylates, nickelchelates, oxalic acid diamides, other hindered amine light stabilizers;other additives such as metal deactivators, phosphites and phosphonites,peroxide decomposers, fillers and reinforcing agents, plasticizers,lubricants, corrosion and rust inhibitors, emulsifiers, mold releaseagents, carbon black, pigments, fluorescent brighteners, both organicand inorganic flame retardants and nondripping agents, melt flowimprovers and antistatic agents. Numerous examples of suitable additivesof the above type are given in Canadian Patent 1,190,038.

Thus, the compounds of this invention are efficient light stabilizersfor both natural and artificial polymeric compositions also providingthe thermal stability usually associated with the hydrazidefunctionality. In addition, the hydrazide functionality permits furtherderivatives to be prepared. The ability to prepare further derivativespermits further modification of the stabilizer properties. These includegreater compatability with the polymeric composition in which it isintended to be incorporated and frequently greater efficiency. Thehydrazide group reacts readily with many functional groups contained inpolymeric or monomeric compounds, such as anhydrides, esters, ketones,aldehydes, chloroformates, acid halides and isocyanates.

Preparative Methods

The novel HALS hydrazides are prepared by reacting (2,2,6,6-tetraalkylpiperidinyl)esters with a primary or secondary alkylhydrazine, hydrazine or hydrazine hydrate. The reaction is illustratedby the following equations. ##STR7## where R¹, R², R¹⁸ and X are aspreviously defined and R is alkyl of 1 to 20 carbons or phenyl.

Typically the ester is dissolved in a polar solvent and converted to thedesired hydrazide by stirring with an equivalent amount or slight excessof a primary or secondary alkylhydrazine, hydrazine or hydrazinehydrate. The reaction may go at room temperature or may require heating.Preferably the hydrazinolysis reaction is carried out in methanol orethanol at 10°-30° C. but other solvents such as isopropanol or ethyleneglycol are also acceptable. In most cases the resulting hydrazides canbe purified by recrystallization from the lower alcohols.

The starting esters are known in the literature as described in U.S.Pat. No. 3,941,744, U.S. Pat. No. 3,975,462, U.S. Pat. No. 4,005,094,U.S. Pat. No. 4,241,208, U.S. Pat. No. 4,408,051, U.S. Pat. No.4,526,966, U.S. Pat. No. 4,562,220, U.S. Pat. No. 4,689,416, U.S. Pat.No. 4,745,192, U.S. Pat. No. 4,755,602 and DE 3,523,679.

Examples of suitable hydrazines include hydrazine, hydrazine hydrate35-85% hydrazine hydrate, methylhydrazine, ethylhydrazine,propylhydrazine, isopropylhydrazine, n-butylhydrazine,sec-butylhydrazine, n-amylhydrazine, sec-amylhydrazine, n-hexylhydrazineand n-octylhydrazine and sec-octylhydrazine.

Hydrazone derivatives of this invention are prepared by reacting thehydrazides with ketones, aldehydes or formaldehyde in inert solvents,preferably in hydrocarbon solvents under azeotropic conditions. ##STR8##where R¹, R², R²⁰, R²¹ and X are as previously defined.

They may also be prepared by reacting hydrazones of ketones or aldehydeswith esters described in the literature (cited above). ##STR9## whereR¹, R², R²⁰, R²¹, R and X are as previously defined.

The novel carbamoyl and thiocarbamoyl derivatives are prepared byreacting the hydrazides with isocyanates, diisocyanates, isothiocyanatesor diisothiocyanates in aprotic polar solvents such as tetrahydrofuranor dimethylformamide. ##STR10## where R¹, R², R¹⁸, R²⁵ and X are aspreviously defined.

The reactions of hydrazides with ketones, aldehydes, isocyanates,diisocyanates, isothiocyanates, and diisothiocyanates are well known inthe art and can occur under a wide variety of temperatures, times,solvents and concentrations. Generally a mole ratio of 0.9 to 1.0 to 1.1to 1.0 of the hydrazide to the monofunctinal coreactant is employed. Ifthe coreactant is difunctional, then a mole ratio of 1.8 to 2.0 to 1.1to 1.0 of the hydrazide to the difunctional coreactant is employed. Ifthe coreactant is a compound that can easily be removed from theproduct, e.g. acetone or methyl ethyl ketone, lower mole ratios may bedesireable. In fact it may be desireable to use the coreactant as thesolvent.

The hydrazides also react with unsubstituted or N-substituted amic acidesters in lower alcohol solutions to form diacyl hydrazines. ##STR11##where R¹, R², R²², R²⁴ (defined as --NH--R¹⁸ in this case and X are aspreviously defined.

The reactions are normally carried out in refluxing alcohol (i.e.methanol) but may be carried out in higher boiling aprotic solvents orwithout solvent by heating a mixture of the two components above theirmelting points. The methyl and ethyl esters of N-substituted oxamatesand succinamates are the preferred coreactants.

The novel acyl derivatives of the hydrazide may be prepared by reactingthe esters (cited in the literature, as above) with acid hydrazides inrefluxing alcohol (i.e. methanol). ##STR12## where R¹⁸, R¹, R², R³, R¹⁹and X are as previously defined.

The novel acyl derivatives may also be prepared by reacting thehydrazides with non-cyclic carboxylic acid anhydrides: ##STR13## whereR¹, R², R¹⁸ and X are as previously defined. The reactions are typicallyconducted in aprotic solvents, such as tetrahydrofuran, diethyl ether ort-butyl methyl ether. However, the reaction may also be carried out byadding the anhydride to a methanolic solution of the hydrazide. Inaddition, when R¹ is hydrogen, alkyl, cycloalkyl, aralkyl or aryl, thecarboxylic acid generated in the reaction may form a salt with thehindered amine. The free base derivatives may be regenerated from thecarboxylic acid salt by neutralizing the salt with a stronger base thanthe hindered amine, for example, dilute sodium hydroxide, dilutepotassium hydroxide, hydrazine or more basic amines, such asdiethylamine or triethylamine.

The corresponding diacyl derivatives can be prepared by reacting theesters with diacid dihydrazides in a 2 to 1 mole ratio in refluxingalcohol (i.e. methanol). ##STR14## where R, R¹, R², R³, R²⁵ and X are aspreviously defined.

The novel alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl andaralkoxycarbonyl derivatives of the hdyrazides may be prepared byreacting the ester (as described above) with the corresponding alkyl,cycloalkyl, aryl or aralkyl carbazates in refluxing alcohol (i.e.methanol). ##STR15## where R, R¹, R², R³, R¹⁸ and X are as previouslydefined.

Alternately, these derivatives may be prepared by reacting the hydrazidewith a disubstituted carbonate or substituted haloformate. When ahaloformate is used, an additional base may be used to react with thehalogen acid formed. The amine group in the molecule may serve thispurpose, but must then be released from its salt form by subsequentreaction with a strong base (as during workup). ##STR16## where R¹, R²,R¹⁸ and X are as previously defined and Y is aryloxy or halogen.

The novel dialkoxycarbonyl, dicycloalkoxycarbonyl, diaryloxycarbonyl anddiaralkoxycarbonyl derivatives of the hydrazide may be prepared byreacting the esters of the literature with the correspondingbiscarbazates. ##STR17##

where R, R¹, R², R³, R²⁵ and X are as previously defined.

The novel sulfonyl derivatives of the hydrazide may be prepared byreacting the esters of the literature with the corresponding sulfonylhydrazide or bis(sulfonyl hydrazides). ##STR18## where R¹, R², R³, R¹⁹,R²⁵ and X are as previously defined.

The novel alkyl derivatives of the hydrazide may be prepared by reactingthe hydrazides with epoxides. The reactions are generally carried outneat or in a minimum amount of a high boiling solvent. Reactiongenerally occurs quite readily at 140°-150° C. ##STR19## where R¹, R²and X are as previously defined and T and T' are selected from groupsnecessary to conform to the definitions of R¹⁸, R¹⁷ and R¹ (whenapplicable).

The hydrazide group reacts with two equivalents of epoxide. If thehindered amine is not substituted, it will also react with the epoxideto give a trialkylated product. The ratio of the unsubstituted hydrazideto the monoalkylated, dialkylated and trialkylated products is dependentupon the the mole ratio of epoxide to hydrazide, the temperature and theconcentration if the reaction is run in a solvent.

Examples of suitable ketones include acetone, methyl ethyl ketone,2-pentanone, 2-hexanone, 3-hexanone, 2-decanone, 3-methyl-2-pentanone,4-methyl-2-pentanone, 4-methoxy-4-methyl-2-pentanone, cyclopentanone,cyclohexanone, 2,4-dimethyl-4-heptanone, 3,5-dimethyl-4-heptanone,2,4-dimethyl-3-pentanone, 1,3-diphenylacetone, 2-octanone, 3-octanone,dihydroisophorone, 4-t-butylcyclohexanone, methyl cyclohexyl ketone,acetophenone, 2,2,6,6-tetramethyl-4-piperidone, andd2,6-diethyl-2,3,6-trimethyl-4-piperidone.

Examples of suitable aldehydes include formaldehyde, acetaldehyde,butyraldehyde, dodecyl aldehyde, 2-ethylbutyraldehyde, heptaldehyde,isobutyraldehyde, isovaleraldehyde, octyl aldehyde, propionaldehyde,benzaldehyde, 3,5-di-t-butyl-4-hydroxybenzaldehyde,2,3-dimethyl-p-anisaldehyde, 3-hydroxybenzaldehyde, 1-naphthaldehyde,salicylaldehyde, p-tolualdehyde and 2,3,4-trimethoxybenzaldehyde.

Examples of suitable isocyanates include allyl isocyanate, benzylisocyanate, n-butyl isocyanate, sec-butyl isocyanate, isobutylisocyanate, t-butyl isocyanate, cyclohexyl isocyanate, ethyl isocyanate,isopropyl isocyanate, 4-methoxyphenyl isocyanate, methyl isocyanate,octadecyl isocyanate, 1-naphthyl isocyanate, phenyl isocyanate, o-tolylisocyanate, m-tolyl isocyanate and p-tolyl isocyanate,dimethyl-m-isopropenylbenzyl isocyanate and 2-isocyanatoethylmethacrylate.

Examples of suitable isothiocyanates include allyl isothiocyanate,benzyl isothiocyanate, 4-bromophenyl isothiocyanate, n-butylisothiocyanate, sec-butyl isothiocyanate, isobutyl isothiocyanate,t-butyl isothiocyanate, 3-chlorophenyl isothiocyanate, cyclohexylisothiocyanate, ethyl isothiocyanate, methyl isothiocyanate, propylisothiocyanate, isopropyl isothiocyanate, 1-naphthyl isothiocyanate,t-octyl isothiocyanate, phenethyl isothiocyanate, phenyl isothiocyanate,propyl isothiocyanate, o-tolyl isothiocyanate, m-tolyl isthiocyanate andp-tolyl isothiocyanates.

Examples of suitable diisocyanates include ethylene diisocyanate,1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate,cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate andmixtures thereof,1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophoronediisocyanate), 2,4-hexahydrotoluene diisocyanate and2,6-hexahydrotoluene diisocyanate and mixtures thereof,hexahydro-1,3-phenylene diisocyanate and hexahydro-1,4-phenylenediisocyanate and mixtures thereof,3,3'-dimethoxybiphenyl-4,4'-diisocyanate,3,3'-dimethylbiphenyl-4,4'-diisocyanate, perhydro-2,4'-diphenylmethanediisocyanate and perhydro-4,4'-diphenylmethane diisocyanate and mixturesthereof, 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate andmixtures thereof, 2,4-tolylene diisocyanate and 2,6-tolylenediisocyanate and mixtures thereof, diphenylmethane-2,4'-diisocyanate anddiphenylmethane-4,4'-diisocyanate and mixtures thereof,naphthylene-1,5-diisocyanate, m-di(2-methyl-2-isocyanatoethyl)benzeneand p-di(2-methyl-2-isocyanatoethyl)benzene and mixtures thereof,2,2,4-trimethylhexamethylene diisocyanate and2,4,4-trimethylhexamethylene diisocyanate.

Examples of suitable diisothiocyanates include ethylenediisothiocyanate, 1,4-tetramethylene diisothiocyanate, 1,6-hexamethylenediisothiocyanate, 1,4-di(isothiocyanato)benzene,1,1'-methylenebis(4-isothiocyanatocyclohexane) and1,1'-oxybis(4-isothiocyanatobenzene).

Examples of suitable amic acid esters include methyl oxamate, ethyloxamate, propyl oxamate, isopropyl oxamate, n-butyl oxamate, phenyloxamate, methyl succinamates, ethyl succinamate, propyl succinamate,isopropyl succinamate, n-butyl succinamate, phenyl succinamate, ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate, methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate, ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)succinamate, methylN-(2,2,6,6-tetramethyl-4-piperidinyl)succinamate, ethylN-(3,5-di-t-butyl-4-hydroxyphenyl)oxamate, methylN-(3,5-di-t-butyl-4-hydroxyphenyl)oxamate, ethylN-(3,5-di-t-butyl-4-hydroxyphenyl)succinamate and methylN-(3,5-di-t-butyl-4-hydroxyphenyl)succinamate.

Examples of suitable acid hydrazides include acetyl hydrazide, propionichydrazide, butyric hydrazide, isobutyric hydrazide, valeric hydrazide,isovaleric hydrazide, caproic hydrazide, decanoic hydrazide, laurichydrazide, stearic hydrazide, benzhydrazide,3,5-di-t-butyl-4-hydroxybenzhydrazide,3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid hydrazide,3-(n-hexylthio)propionic acid hydrazide,(4-benzoyl-3-hydroxyphenoxy)acetyl hydrazide, and3-(dimethylaminoethylthio)propionic acid hydrazide.

Examples of suitable diacid dihydrazides include succinic acidhydrazide, adipic acid dihydrazide, azelaic acid dihydrazide,dodecanedioic acid dihydrazide and 1,3-benzenedicarboxylic aciddihydrazide and 1,4-benzenedicarboxylic acid dihydrazide.

Examples of suitable carbazates include ethyl carbazate, methylcarbazate, propyl carbazate, isopropyl carbazate, butyl carbazate,cyclohexyl carbazate, cyclopentyl carbazate, cyclododecyl carbazate,phenyl carbazate, benzyl carbazate, 4-t-butylcyclohexyl carbazate,2-ethylhexyl carbazate, 4-methylphenyl carbazate and 3-methoxyphenylcarbazate.

Examples of bis(carbazates) include ethylenebis(carbazate),cyclohexane-1,2-diylbis(carbazate), cyclohexane-1,4-diylbis(carbazate),decane-1,10-diylbis(carbazate),2,2-diethylpropane-1,3-diylbis(carbazate),2,2-dimethyl-1,3-diylbis(carbazate), hexane-1,6-diylbis(carbazate) andpropane-1,3-diylbis(carbazate).

Examples of suitable diaryl carbonates include diphenyl carbonate,di-(4-methylphenyl) carbonate, di-(3-methylphenyl) carbonate,di-(3-methoxyphenyl) carbonate, di-(2,6-dimethylphenyl) carbonate anddi-(2,5-di-t-butylphenyl) carbonate.

Examples of suitable sulfonyl halides include benzenesulfonyl hydrazide,4-bromobenzenesulfonyl hydrazide, 1-butanesulfonyl hydrazide,4-t-butylbenzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide,ethanesulfonyl hydrazide, methanesulfonyl hydrazide,4-fluorobenzenesulfonyl hydrazide, 1-hexadecanesulfonyl hydrazide,isopropanesulfonyl hydrazide and 1-naphthalenesulfonyl hydrazide.

Examples of suitable bis(sulfonyl hydrazides) include1,3-benzenebis(sulfonyl hydrazide), 1,4-benzenebis(sulfonyl hydrazide),1,2-ethanebis(sulfonyl hydrazide), 1,4-butanebis(sulfonyl hydrazide),1,1'-oxybis(benzenesulfonyl hydrazide),1,1'-methylenebis(benzenesulfonyl hydrazide) and1,4-cyclohexanebis(sulfonyl hydrazide).

Examples of suitable epoxides include 1,2-epoxybutane, 2,3-epoxybutane,1,2-epoxycyclododecane, 1,2-epoxycyclohexane, 1,2-epoxyoctane,1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxyoctadecane,1,2-epoxy-3-phenoxypropane, 2,3-epoxypropyl acrylate, 2,3-epoxypropylmethacrylate, 2,3-epoxypropyl 4-methoxyphenyl ether, glycidyl isopropylether, glycidyl n-hexyl ether, glycidyl dodecyl ether and glycidyloctadecyl ether.

The following examples are presented to further illustrate the best modecontemplated by the inventor for practicing the present invention andare intended as illustrations and not as limitations of the invention.

EXAMPLE 120-(3-hydrazino-3-oxopropyl)-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

20-(3-Dodecyloxy-3-oxopropyl)-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-22-one(Sanduvor 3050™), 66.5g (0.11 mole) was placed in a flask and dissolvedwith 150 ml methanol. To this was added 35 ml of hydrazine (54% inwater) producing an immediate white precipitate. The mixture was stirredat ambient temperature for 28 hours. Most of the solvent was strippedusing aspirator vacuum and the residue taken up in 100 ml methyl t-butylether and 175 ml tetrahydrofuran. The aqueous layer which separated wasremoved and the organic phase washed with three 50 ml portions ofsaturated sodium chloride. The organic material was dried with anhydrousmagnesium sulfate, and the solvent was stripped using aspirator vacuum.The white semi-solid residue was slurried with pentane and isolated. Theproduct weighed 39.4 g (79% of theory) and had two melting points at171°-174° C. and 185° C. The infrared spectrum (in chloroform) showed acarbonyl band at 1680 cm⁻¹.

EXAMPLE 220-[5-(2,2,6,6-tetramethylpiperidine-4-ylidene)-4,5-diaza-oxopentyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadi-spiro[5.1.11.2]heneicosane-21-one

The hydrazide of Example 1, 2.25 g (0.005 mole),2,2,6,6-tetramethyl-4-piperidone monohydrate, 0.85 g (0.005 mole),p-toluenesulfonic acid, 0.08 g, and 100 ml xylenes were combined in aflask fitted with a Dean Stark water separation assembly. The reactionmixture was heated to reflux for 3 hours with azeotropic removal ofwater as it formed. The mixture was cooled and transferred to aseparatory funnel and washed with 25 ml 5% sodium bicarbonate. Theorganic material was isolated and stripped of solvent using aspiratorvacuum yielding a tan residue. Analysis showed residual startinghydrazide was present. The product was put back in a flask with2,2,6,6-tetramethyl-4-piperidone monohydrate, 0.42 g, p-toluenesulfonicacid, 0.05 g, and 100 ml xylenes. This mixture was heated to reflux foran hour with water removal. The reaction mixture was cooled andtransferred to a separatory funnel, washed with 25 ml 5% sodiumbicarbonate and the solvent stripped using aspirator vacuum. The residuewas recrystallized from toluene yielding 1.9 g of white crystals (66% oftheory), melting 142°-144° C. The infrared spectrum (in chloroform)showed a single broad carbonyl band at 1685 cm⁻¹. The mass spectrumshowed the molecular ion at m/e 588.

EXAMPLE 320-[5-(3,3,5-trimethylcyclohexylidene)-4,5-diaza-3-oxopentyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[51 11 2]heneicosane-21-one

The hydrazide of Example 1, 2.25 g (0.005 mole),3,3,5-trimethylcyclohexanone, 0.7 g (0.005 mole) and 100 ml xylenes werecombined in a flask fitted with a Dean Stark water separation assembly.The reaction mixture was heated to reflux for 2 hours with azeotropicremoval of water as it formed. At this time, additionaltrimethylcyclohexanone, 0.35 g was added and the reaction continued for30 minutes. The mixture was cooled and stripped of solvent usingaspirator vacuum yielding 2 9 g of tan crystals (99% of theory), melting190°-193° C. The infrared spectrum (in chloroform) showed a single broadcarbonyl at 1680 cm⁻¹. The mass spectrum showed the molecular ion at m/e573.

EXAMPLE 420-[4,5,7-triaza-3,6-dioxopentacosyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadi-spiro[5.1.11.2]heneicosane-21-one

The hydrazide of Example 1, 2.25 g (0.005 mole), octadecyl-isocyanate,1.48 g (0.005 mole) and 100 ml tetrahydrofuran were combined in a flaskunder nitrogen atmosphere. The reaction mixture was heated to reflux for1 hour. The mixture was cooled and stripped of solvent using aspiratorand high vacuum yielding 3.8 g of gummy solid (100% of theory), whichturned to white crystals upon cooling with dry ice. The melting rangewas 40°-45° C. The infrared spectrum (in chloroform) showed a singlebroad carbonyl band at 1685 cm⁻¹. The mass spectrum showed the molecularion at m/e 746.

EXAMPLE 520-[8-(2,2,6,6-tetramethyl-4-piperidinyl)-4,5,8-triaza-3,6,7-trioxooctyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

The hydrazide of Example 1, 2.25 g (0.005 mole), ethyl2-(2,2,6,6-tetramethyl-4-piperidinyl amino)-2-oxoacetate, 2.09 g (0.005mole) and 50 ml methanol were combined in a flask fitted with adistillation head. The mixture was heated to reflux and the solventslowly distilled, removing about 40 ml over 5.5 hours producing a thickpaste. Distillation ceased for an additional 5 hours reflux. Thereaction mixture was cooled and the solid isolated by filtration, usingadditional methanol to rinse the solids. The filtrate was put back inthe reaction flask and heated to reflux distilling all but about 5 mlsolvent over a 3 hour period, forming and precipitating additionproduct. The reaction was again cooled, and the solid isolated. Thesolids were combined and dissolved in 100 ml hot tetrahydrofuran and thehot solution filtered. The solvent was stripped using aspirator and highvacuum to give 1.9 g of white crystals (58% of theory) melting 130°-135°C. The infrared spectrum (in chloroform) showed two carbonyl bands at1665 and 1685 cm⁻¹. The mass spectrum showed the molecular ion at m/e661.

EXAMPLE 620-[4,5-diaza-3,6-dioxo-9-ethyl-7-oxatridecyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro5.1.11.2]heneicosane-21-one

The hydrazide of Example 1, 2.25 g (0.005 mole), was slurried in 35 mltetrahydrofuran and 2-ethylhexyl chloroformate, 0.96 g (0.005 mole) wasadded at ambient temperature producing an exotherm to 35° C. anddissolving the hydrazide. The mixture was heated to reflux for 1 hour.The reaction mixture was cooled and transferred to a separatory funnelwith 100 ml methyl t-butyl ether. The organic mixture was washed withthree 50 ml portions of 10% sodium carbonate and two 50 ml portionswater. The organic material was dried using anhydrous magnesium sulfateand the solvent stripped using aspirator and high vacuum. The residuewas 3.0 g of white crystals (100% of theory) melting 65°-68° C. Theinfrared spectrum (in chloroform) showed two carbonyl bands at 1685 and1750 cm⁻¹. The mass spectrum showed the molecular ion at m/e 607.

EXAMPLE 720-(8-carboxy-4,5-diaza-3,6-dioxoheptacosyl)-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

The hydrazide of Example 1, 4.52 g (0.01 mole), octadecylsuccinicanhydride, 3.50 g (0.01 mole) and 50 ml tetrahydrofuran were combinedand refluxed for 45 minutes. The solution was cooled and stripped ofsolvent using aspirator and high vacuum. A white solid was obtained. Theinfrared spectrum (KBr) showed a broad carbonyl band over the range1620-1710 cm⁻¹ and a broad OH band 2900-3300 cm⁻¹.

EXAMPLE 820-{3-[N-(octadecylsuccinimido)amino]-3-oxopropyl}-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

The hydrazide of Example 7 and 100 ml xylenes were combined in a flaskfitted with a Dean Stark water separation assembly. The reaction mixturewas heated to reflux for 3 hours with azeotropic removal of water as itformed. The xylenes were stripped using aspirator vacuum and theresidual oil was mixed with 100 ml acetone which quickly solidified theoil. The solid was filtered and dried for 1 hour on the filter funnel.The white solid product weighed 4.8 g and had a melting range of105°-110° C. The infrared spectrum (in chloroform) showed two carbonylbands at 1675 and 1730 cm⁻¹. The OH band of the starting amic acid wasnot observed.

EXAMPLE 920-{3-[N-(4-methylhexahydrophthalimido)amino]-3-oxopropyl}-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

The hydrazide of Example 1, 13.5 g (0.03 mole), was added to 225 mlxylene at 75° C. Added dropwise to this was 4-methylhexahydrophthalicanhydride, 5.1 g (0.03 mole) in 25 ml xylene. The apparatus was fittedwith a Dean Stark water separation assembly and the reaction mixture washeated to reflux for 4 hours with azeotropic removal of water as itformed. The xylenes were stripped using aspirator vacuum and theresidual sticky solid was slurried with 300 ml pentane. The solid wasfiltered and dried for 2 hours on the filter funnel. The white solidproduct weighed 11.7 g and had a melting range of 210°-212° C. Theinfrared spectrum (mull) showed two carbonyl bands at 1690 and 1730cm⁻¹.

EXAMPLE 1020-[4,5,7-triaza-3,6-dioxoundecyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one

The hydrazide of Example I, 5.4 g (0.012 mole), butylisocyanate, 1.2 g(0.012 mole), and 50 ml tetrahydrofuran were combined and heated toreflux for 1.5 hours. The mixture was cooled and the precipitatedproduct was filtered and air dried for 4 hours. The product weighed 5.1g (77% of theory) and had melting range 58°-63° C.

EXAMPLE 11 3-(Hydrazinocarbonylmethyl)-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione

A. Ethyl bromoacetate (1.9 g, 0.011 mole), the potassium salt of7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione (2.6 g, 0.010mole) and 30 ml of dimethylformamide were combined in a flask undernitrogen. The mixture was heated to 60° C. for 2.5 hours. The solventwas stripped leaving a solid residue which was dissolved in 100 mlmethylene chloride. The solution was washed with 100 ml of water. Theorganic solution was dried with anhydrous magnesium sulfate and thesolvent removed under vacuum to give 2.2 g of white solid with meltingrange 134°-136° C. The infrared spectrum of the product had threecarbonyl absorption bands at 1715 cm⁻¹, 1750 cm⁻¹ and 1780 cm⁻¹.Additional confirmation of product integrity was obtained from the NMRspectrum. B. The ester prepared above (1.2 g, 0.004 mole) was dissolvedin 50 ml methanol To this was added 54% hydrazine (5 ml) and theresulting solution was stirred for 4 hours. The solvent was removedunder vacuum to yield a gum which was slurried with 50 mltetrahydrofuran and this solvent stripped under vacuum to give 1.1 gwhite solid. this solid as dissolved in methylene chloride and filtered.The solvent was removed under vacuum to give 0.8 g white solid havemelting range 75°-85° C. The infrared spectrum had two carbonylabsorptions at 1720 cm⁻¹ and 1780 cm⁻¹. Additional confirmation ofproduct integrity was obtained from the NMR spectrum and the massspectrum showed the molecular ion at m/e 298.

EXAMPLE 123-(Hydrazinocarbonylmethyl)-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,acetophenone hydrazone

The hydrazide of example 10 (2.0 g, 0.007 mole) and acetophenone (0.8 g,0.007 mole) were combined in 100 ml xylenes in a flask equipped with aDean Stark water separation assembly. The solution was heated to refluxfor 2 hours before the addition of p-toluenesulfonic acid monohydrate(0.07 g). Reflux was continued for 54 hours with azeotropic removal ofwater. Additional acetophenone (0.8 g) was added and reflux continuedfor a total of 76 hours. The solvent and residual acetophenone wereremoved under vacuum with heating to 180° C. to give 2.4 g of slightlyyellow solid having melting range 215°-225° C. The infrared spectrum ofthe product showed merged carbonyl absorptions with peak at 1722 cm⁻¹.

EXAMPLE 13 Evaluation of Tensile Bars Containing HALS Hydrazides orDerivatives

Dry ends of Himont 6501 polypropylene, the HALS stabilizer andoptionally a small amount of a hindered phenol antioxidant (Irganox1076, product of Ciba-Geigy) and/or UV abosrber (UV-Check AM-340,product of Ferro Corp) were prepared in a polyethylene containiner asspecified in Table I. The blends were shaken well to insure a gooddispersion of the additive in the polypropylene. The blends were thenextruded on a Brabender Prep Center Extruder Model No. 1340 having a1.25 inch screw diameter with a length to diameter ratio of 25:1. Theextruder was operated at a screw speed of 30 RPM and all the heatingzones were controlled at 200° C. The first 100 grams of extrudate wereused to purge out the extruder between runs and were discarded. Theremaining extrudate was air-cooled and pelletized. The concentration ofthe 2,2,6,6-tetramethyl-4-piperidinyl group in the polypropylene wasapproximately 0.3%. The concentration of the Irganox 1076, when used,was approximately 0.25%. The concentration of UV-Check AM-340, whenused, was approximately 0.22%.

The pellets were injection molded in a Newbury 25 ton injection moldingmachine at 400° F. into 7+3/8 inch×3/4 inch×1/8 inch tensile bars.

A control sample containing only Irganox 1076 was included forcomparison. Control samples containing Irganox 1076 and eitherChimassorb 944 (HALS product of Ciba Geigy) or Tinuvin 770 (HALS productof Ciba Geigy) were also included for comparison.

The tensile bars were placed in a QUV Accelerated Weathering Tester (QPanel Company) for various exposure times. The QUV contained UV-B bulbsand operated with an 8 hour light cycle at 60° C. and a 4 hourcondensation cycle at 50° C. Samples were withdrawn periodically at thesame time of day. The tensile bars were pulled on an instrumentedInstron according to ASTM Procedure 638. The minimum QUV exposure timerequired to obtain a brittle break in the Instron was determined. Aresult was considered a brittle break when the tensile bar snappedbefore 15% elongation was obtained.

The QUV time interval required to generate spotting and clouding of thesurface of the tensile bars was also noted.

The results indicate that the compounds of this invention are efficientlight stabilizers for polypropylene and in most cases are considerablymore efficient than the commercial light stabilizers against UV-B light.

                                      TABLE I                                     __________________________________________________________________________    Light Stabilizer in Polypropylene Test Formulations                                                               Days                                                           Irg UV-C  Days to                                        Form.         HALS                                                                              PP 1076*                                                                             AM-340+                                                                             To   Brittle                                   No. HALS Additive                                                                           g   g  g   g     Spotting                                                                           Break                                     __________________________________________________________________________    I   Hydrazide of Ex 1                                                                       4.3 445                                                                              0   0     31-34                                                                              21-30                                     II  Hydrazide of Ex 1                                                                       4.3 445                                                                              1.1 0     41-49                                                                              26-30                                     III Hydrazide of Ex 9                                                                       5.7 445                                                                              0   0     <20  <11                                       IV  Hydrazide of Ex 9                                                                       5.7 445                                                                              1.1 0     31-34                                                                              20-25                                     V   Hydrazide of Ex 6                                                                       5.9 445                                                                              1.1 0     50-60                                                                              20-25                                     VI  Hydrazide of Ex 6                                                                       5.9 445                                                                              1.2 1.2   0    >60                                       VII Hydrazide of Ex 10                                                                      5.2 445                                                                              0   0     >35  18-20                                     --  None          445                                                                              1.1 0     --    <5                                       --  Chimassorb 944                                                                              445                                                                              1.1 0      33  21-24                                     --  Tinuvin 770   445                                                                              1.1 0     >35  21-24                                     __________________________________________________________________________     *Irganox 1076, a product of Ciba Geigy                                        +UVCheck AM340, a product of Ferro Corp                                  

I claim:
 1. A compound of the formula ##STR20## where R¹ is hydrogen,oxyl, hydroxyl, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted carbocyclic araliphatic of 7-22 carbons, substituted orunsubstituted aliphatic acyl of 2-20 carbons, substituted orunsubstituted alicyclic acyl of 7-16 carbons, substituted orunsubstituted carbocyclic aromatic acyl of 7-11 carbons, substituted orunsubstituted carbocyclic araliphatic acyl of 7-22 carbons,--(C(═O))_(a) --N(R⁴)(R⁵), --(C(═O))_(a) --O--R⁶, --(CH₂)_(a)--C(═O)--O--R⁷ where is a 1-2, or --(CH₂ --CH(R⁸)--O)_(b) --R⁹ where bis 2-50;R² is hydrogen or aliphatic of 1-4 carbons; R³ is hydrogen,substituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted carbocyclic araliphatic of 7-22 carbons or substituted orunsubstituted alicyclic of 5-12 carbons; R⁴ and R⁵ are independentlyhydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted carbocyclic aryl of 6-14 carbons,substituted or unsubstituted carbocyclic araliphatic of 7-22 carbons orsubstituted or unsubstituted alicyclic of 5-12 carbons which mayoptionally contain --N(R¹⁰)-- as a ring member with the proviso thatbonding to the amide nitrogen to which R⁴ and R5 are attached is througha carbon atom, or R⁴ and R⁵ may be linked together through --N(R¹⁰)-- or--O-- to form a heterocyclic ring including the nitrogen atom to whichthey are attached of 5-7 atoms with the proviso that the --N(R¹⁰)-- or--O-- linking R⁴ and R⁵ must be separated from the nitrogen atom towhich R⁴ and R⁵ are attached by at least one carbon atom; R⁶ issubstituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted alicyclic of 5-12 carbons, substituted or unsubstitutedcarbocyclic aryl of 6-14 carbons or substituted or unsubstitutedcarbocyclic araliphatic of 7-22 carbons, R⁷, R⁸ and R⁹ are independentlyhydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted carbocyclic aryl of 6-14 carbons or substituted orunsubstituted carbocyclic araliphatic of 7-22 carbons, R¹⁰ is hydrogen,substituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted alicyclic of 5-20 carbons, substituted or unsubstitutedcarbocyclic araliphatic of 7-22 carbons, substituted or unsubstitutedaliphatic acyl of 2-20 carbons, substituted or unsubstituted alicyclicacyl of 7-16 carbons, substituted or unsubstituted carbocyclic aromaticacyl of 7-11 carbons, substituted or unsubstituted carbocyclicaraliphatic acyl of 7-22 carbons, --(C(═O))_(a) --N(R⁴)(R⁵),--(C(═O))_(a) --O--R⁶, --(CH₂)_(a) --C(═O)--O--R⁷ where a is 1-2, or--(CH₂ --CH(R⁸)--O)_(b) --R⁹ were b is 2-50, X is a triradical ##STR21##R¹¹ is independently of the same definition as R⁷ and when alicyclic mayoptionally contain --N(R¹⁰)-- as a ring member, with the proviso thatbonding to the nitrogen atom to which "R" is attached must be through acarbon atom; R¹² is substituted or unsubstituted aliphatic diradical of1-20 carbons, substituted or unsubstituted carbocyclic aryl diradical of6-12 carbons, substituted or unsubstituted alicyclic diradical of 5-12carbons or substituted and unsubstituted carbocyclic araliphaticdiradical of 7-22 carbons and the diradicals may optionally contain 1-6heteroatoms --O--, --S--, and --N(R¹⁰)-- with the proviso that multipleheteroatoms must be separated from each other by at least two carbonatoms and from the diradical ends by at least one carbon atom; R¹³ isindependently of the same definition as R⁶ ; R¹⁴ is independently of thesame definition as R¹², and when Y is a direct bond, R¹⁴ may also be adirect bond; R¹³ and R¹⁴ together with the carbon atom linking them mayform a substituted or unsubstituted cycloalkyl ring of 5-12 carbons, R¹⁵and R¹⁶ are independently of the same definition as R¹¹ and may also becarbamoyl, alkoxycarbonyl of 2-5 carbons or pyridyl, and R¹⁵ and R¹⁶ maybe linked together to form an alicyclic of 5-12 carbons, or may belinked together through a heteroatom --O--, --S--, and --N(R¹⁰)-- toform a heterocyclic ring including the carbon atom to which they areattached of 5-7 atoms with the proviso that multiple heteroatoms must beseparated from each other by at least two carbon atoms; Y is --O--,--N(R¹¹)-- or a direct bond; n is 1 or 2; when n is 1, Z is ##STR22##when n is 2, Z is ##STR23## R¹⁷ is independently of the same definitionas R¹¹, R¹⁸ is independently of the same definition as R¹¹, Q is--C(═O)--, --S(═O)₂ --, --C(═O)--O--, --[C(═O)]₂ --O--,--C(═O)--N(R¹⁰)--, --[C(═O)]₂ --N(R¹⁰)--, --C(═S)--N(R¹⁰)--,--C(═O)--R²² --C(═O)--N(R¹⁰)-- or, when n is 1, a direct bond betweenthe nitrogen and R¹⁸, R¹⁹ and R²⁰ are independently of the samedefinition as R¹¹, and R¹⁹ and R²⁰ may be linked together to form asubstituted or unsubstituted alicyclic ring of 5-12 carbons or may belinked together through a heteroatom --N(R¹⁰)--, --O-- and --S-- to forma heterocyclic ring including the carbon atom to which they are attachedof 5-12 atoms, R²¹ is substituted or unsubstituted aliphatic diradicalof 2-2000 carbons, substituted or unsubstituted carbocyclic aryldiradical of 6-14 carbons, substituted or unsubstituted alicyclicdiradical of 5-12 carbons or substituted or unsubstituted carbocyclicaraliphatic diradical of 7-22 carbons, and the diradical chain(s) mayoptionally contain 1-6 heteroatoms --O--, --S-- and --N(R¹⁰)-- with theprovisos that (a) multiple heteroatoms must be separated from each otherby at least two carbon atoms and from the chain ends by at least onecarbon atom, and that (b) the cyclic group formed contains 5-6 atoms inthe ring, R²² is a direct bond or is a substituted or unsubstitutedaliphatic diradical of 1-200 carbons, substituted or unsubstitutedcarbocyclic aryl diradical of 6-14 carbons, substituted or unsubstitutedalicyclic diradical of 5-22 carbons or substituted or unsubstitutedcarbocyclic araliphatic diradical of 7-22 carbons, and the diradicalchain(s) may optionally contain 1-6 heteroatoms --O--, --S--, and--N(R¹⁰)-- with the proviso that multiple heteroatoms must be separatedfrom each other by at least two carbon atoms and from the chain ends byat least one carbon atom, R²³ is independently of the same definition asR¹¹, R²⁴ is chosen from --NH(R¹⁸), --OH and O⁻ M⁺, where M⁺ is sodiumion, potassium ion or ammonium ion, R²⁵ is substituted or unsubstitutedaliphatic diradical of 1-20 carbons, substituted or unsubstituted aryldiradical of 6-12 carbons, substituted or unsubstituted alicyclicdiradical of 5-12 carbons or substituted or unsubstituted carbocyclicaraliphatic diradical of 7-22 carbons, and the diradical chain(s) mayoptionally contain 1-6 heteroatoms selected from --O-- and --N(R¹⁰)--with the proviso that multiple heteroatoms must be separated from eachother by at least two carbon atoms and from the chain ends by at leastone carbon atom, and optional substitutents for R¹, R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²²,R²³ and R²⁵ are one or more of the following: chloro, bromo, alkyl of1-8 carbons, alkoxy of 1-12 carbons, phenoxy, cyano, hydroxy, epoxy,carboxy, benzoyl, benzoyloxy, dialkylamino of 2-8 carbons total,alkyoxycarbonyl of 2-6 carbons, acyloxy of 1-4 carbons, acryloyl,acryloyloxy, methacryloyl, methacryloyloxy, hydroxymethyl, hydroxyethyl,alkylthio of 1-4 carbons and trialkoxysilyl of 3-12 carbons; andadditional optional substituents for R²¹ and R²² are alkyl of 5-180carbons, alkylthio of 5-180 carbons, carbocyclic aralkylthio of 7-20carbons, carbocyclic arylthio of 6-20 carbons, alkenyl of 2-180 carbons,cycloalkenyl of 5-12 carbons, carbocyclic aryl of 6-16 carbons,carbocyclic aralkyl of 7-17 carbons, carbocyclic aryloxy of 6-16carbons, alkoxycarbonyl of 7-10 carbons, and (alkoxycarbonyl)alkylthioof 3-30 carbons; and additional substituents for R¹⁸ are chosen fromaliphatic of 1-20 carbons, cycloaliphatic of 5-12 carbons, carbocyclicaryl of 6-14 carbons, carbocyclic aralkyl of 7-22 carbons, alkoxy of1-20 carbons, cycloalkoxy of 5-12 carbons, carbocyclic aryloxy of 6-14carbons, carbocyclic aralkoxy of 7-15 carbons, aliphatic acyloxy of 2-20carbons, alicyclic acyloxy of 6-13 carbons, carbocyclic aromatic acyloxyof 7-15 carbons, and carbocyclic araliphatic acyloxy of 8-16 carbons. 2.A compound as defined in claim 1 whereinR¹ is hydrogen, substituted orunsubstituted aliphatic of 1-4 carbons, substituted or unsubstitutedcarbocyclic araliphatic of 7-10 carbons, substituted or unsubstitutedaliphatic acyl of 2-6 carbons or substituted or unsubstituted benzoyl,R² is hydrogen or methyl, R³ is hydrogen, R⁴ and R⁵ are independentlyhydrogen, substituted or unsubstituted aliphatic of 1-8 carbons,substituted or unsubstituted phenyl or substituted or unsubstitutedbenzyl, R⁶ is substituted or unsubstituted aliphatic of 1-8 carbons,substituted or unsubstituted phenyl or substituted or unsubstitutedbenzyl, R⁷, R⁸ and R⁹ are independently hydrogen, substituted orunsubstituted aliphatic of 1-8 carbons, substituted or unsubstitutedphenyl or substituted or unsubstituted benzyl, R¹⁰ is hydrogen,substituted or unsubstituted aliphatic of 1-4 carbons, substituted orunsubstituted carbocyclic araliphatic of 7-10 carbons, substituted orunsubstituted aliphatic acyl of 2-6 carbons or substituted orunsubstituted benzoyl, R¹⁵ and R¹⁶ are independently substituted orunsubstituted aliphatic of 1-20 carbons, substituted or unsubstitutedalicyclic of 5-6 carbons, substituted or unsubstituted carbocyclic arylof 6-10 carbons, substituted or unsubstituted carbocyclic araliphatic of7-16 carbons, or may be linked together to form an alicyclic of 5-22carbons or may be linked together to form a group of formula ##STR24##R¹⁸ is selected from hydrogen, substituted or unsubstituted aliphatic of1-12 carbons, substituted or unsubstituted alicyclic of 5-8 carbons,substituted or unsubstituted phenyl or substituted or unsubstitutedcarbocyclic araliphatic of 7-9 carbons and when alicyclic R¹⁸ mayoptionally contain 1-2 heteroatoms selected from --O-- and --N(R¹⁰)--with the proviso stated in claim 1, Q is --C(═O)--, --C(═O)--O--,--[C(═O)]₂ --O--, --C(═O)--N(R¹⁰)--, --[C(═O)]₂ --N(R¹⁰)-- or, when n is1, a direct bond between the nitrogen and R¹⁸, R¹⁹ and R²⁰ areindependently substituted or unsubstituted aliphatic of 1-8 carbons,substituted or unsubstituted alicyclic of 5-8 carbons, substituted orunsubstituted carbocyclic aryl of 6-12 carbons or substituted orunsubstituted carbocyclic araliphatic of 7-14 carbons, and R¹⁹ and R²⁰may be linked together to form a substituted or unsubstituted cycloalkylring of 5-8 carbons or a group of formula ##STR25## R²¹ is substitutedor unsubstituted aliphatic diradical of 2-18 carbons, substituted orunsubstituted ortho-phenylene or substituted or unsubstituted alicyclicdiradical of 6-8 carbons, and the diradical chain(s) may optionallycontain 1-2 heteroatoms --O-- and --N(R¹⁰)-- with the proviso stated inclaim 1, R²² is substituted or unsubstituted aliphatic diradical of 2-18carbons, substituted or unsubstituted phenylene or substituted orunsubstituted alicyclic diradical of 6-8 carbons, and the diradicalchain(s) may optionally contain 1-2 heteroatoms, --O-- and --N(R¹⁰)--with the proviso stated in claim 1, R²⁴ is --OH or --O⁻ M⁺ where M issodium ion, R²⁵ is substituted or unsubstituted aliphatic diradical of2-12 carbons, substituted or unsubstituted aryl diradical of 6-12carbons, substituted or unsubstituted alicyclic diradical of 5-12carbons or substituted or unsubstituted araliphatic diradical of 7-12carbons, and the diradical chain(s) may optionally contain 1-2heteroatoms selected from --O-- and --N(R¹⁰)-- with the proviso statedin claim
 1. 3. A compound as defined in claim 2 whereinR¹ is hydrogen,methyl, acetyl or benzoyl, R² is hydrogen, R⁴ is hydrogen, methyl orethyl, R⁵ is substituted or unsubstituted aliphatic of 1-8 carbons, orsubstituted or unsubstituted phenyl, R¹⁰ is hydrogen, methyl, acetyl orbenzoyl, R¹⁷ is hydrogen, substituted or unsubstituted aliphatic of 1-10carbons, substituted or unsubstituted cyclohexyl, substituted orunsubstituted phenyl or substituted or unsubstituted carbocyclicaraliphatic of 7-14 carbons, R¹⁸ is selected from hydrogen, substitutedor unsubstituted aliphatic of 1-10 carbons, substituted or unsubstitutedcyclohexyl, substituted or unsubstituted phenyl or substituted orunsubstituted carbocyclic araliphatic of 7-14 carbons and when alicyclicR¹⁸ may be substituted piperidin-4-yl, R²⁴ is --OH, R²⁵ is substitutedor unsubstituted aliphatic diradical of 2-10 carbons, substituted orunsubstituted phenylene, substituted or unsubstituted alicyclicdiradical of 5-8 carbons or substituted or unsubstituted carbocyclicaraliphatic diradical of 7-12 carbons.
 4. A compound as defined in claim2 wherein R¹⁷ is hydrogen, substituted or unsubstituted aliphatic of1-12 carbons, substituted or unsubstituted alicyclic of 5-8 carbons,substituted or unsubstituted phenyl, or substituted or unsubstitutedcarbocyclic araliphatic of 7-9 carbons.
 5. A compound as defined inclaim 3 which is20-(3-hydrazino-3-oxopropyl)-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro[5.1.11.2]heneicosane-21-one.6. A compound as defined in claim 3 which is20-[5-(2,2,6,6-tetramethylpiperidine-4-ylidene)-4,5-diaza-3-oxopentyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one.7. A compound as defined in claim 1 which is20-[5-(3,3,5-trimethylcyclohexylidene)-4,5-diaza-3-oxopentyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[51.11.2]heneicosane-21-one.
 8. A compound as defined in claim 1 which is20-[4,5,7-triaza-3,6-dioxopentacosyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadi-spiro[5.1.11.2]heneicosane-21-one.9. A compound as defined in claim 2 which is20-[8-(2,2,6,6-tetramethyl-4-piperidinyl)-4,5,8-triaza-3,6,7-trioxooctyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one.10. A compound as defined in claim 3 which is20-[4,5-diaza-3,6-dioxo-9-ethyl-7-oxatridecyl]-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one.11. A compound as defined in claim 3 which is20-(8-carboxy-4,5-diaza-3,6-dioxoheptacosyl)-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one.12. A compound as defined in claim 3 which is20-{3-[N-(octadecyl-succinimido)amino]-3-oxopropyl}-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one.13. A compound as defined in claim 3 which is20-{3-[N-(4-methyl-hexahydrophthalimido)amino]-3-oxopropyl}-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one.